Elements of the Sea

Ionic equations
o If 2 solutions react to form a solid, a precipitation reaction occurs. Eg. Ag+(aq) + No3 (aq) + Na+(aq) + !r (aq) goes to Ag!r(s) + Na+"aq# + N$3 (aq) %hen cancel spectators Ag+(aq) + !r (aq) goes to Ag!r(s) o Al&a's include state s'm(ols o $nl' split into ions if aqueous and ionic

Ionic solids
o )ations and anions are held together (' strong electrostatic attractions in a giant ionic lattice. o Each sodium ion is surrounded (' * chloride ions *+* coordination. It is a simple cu(ic structure. o Ionic solids are hard and ha,e a high melting point due to strong electrostatic attractions (et&een ions. o If ionic cr'stals contain &ater, the &ater molecules fit into the lattice the same &a' as regular ions. %his is called the &ater of cr'stallisation. %hese cr'stals are said to (e h'drated. o If these h'drated cr'stals are heated, the &ater molecules are dri,en off and 'ou are left &ith an anh'drous solid.

Ionic su(stances in solution

o As ionic su(stances dissol,e in &ater, the ions (ecome surrounded (' &ater molecules and the' spread throughout the solution. %he h'drated ions are randoml' arranged and (eha,e independentl'.

o -ater surrounds the ions in this &a' (ecause it is polar and (ent. %he partiall' + . ions are attracted to the partiall' negati,e ions. o In positi,e ions, the &ater molecules surround the ion &ith the o/'gen atoms pointing in&ards, and &ith the h'drogen atoms pointing in&ards in negati,el' charged ions.

0ules on solu(ilit'
Soluble salts All sodium, potassium and ammonium salts. Nitrates are al&a's solu(le 1ost chlorides, (romides and iodides. 1ost sulphates. Insoluble salts All car(onates are insolu(le e/cept for sodium, potassium and ammonium car(onates. Sil,er and lead chlorides, (romides and iodides. )alcium, strontium and (arium sulphate.

)harges on ions
Positive ions (cations) .'drogen .+ Sodium Na+ Sil,er Ag+ 3otassium 4+ 5ithium 5i+ Ammonium N.6+ !arium !a2+ )alcium )a2+ )opper(II) )u2+ 7inc 7n2+ 1agnesium 1g2+ 5ead 3(2+ Iron(II) 2e2+ Iron(III) 2e3+ Aluminium Al3+ Negative ions (anions) )hloride )l !romide !r 2luoride 2 Iodide I .'drogencar(onate .)$3 .'dro/ide $. Nitrate N$3 $/ide $2 Sulphide S2 Sulphate S$62 )ar(onate )$32

Atoms and ions

2irst ionisation enthalp'

o %he energ' needed to remo,e one electron from e,er' atom in a mole of gaseous atoms. o $ne mole of gaseous ions &ith one positi,e charge is formed. 8(g) goes to 8+(g) + e o 9nits are :;mol < and 2IE is al&a's positi,e as energ' must (e put in to remo,e the electron as it is attracted to the positi,e nucleus. o %he pea:s are elements in group # (no(le gases). It is difficult to remo,e an electron from these atoms (ecause the' ha,e full outer shells and are unreacti,e. o %he troughs are elements in group <. %hese onl' ha,e < outer shell electron so are eas' to ionise and are ,er' reacti,e. o It (ecomes harder to remo,e an electron across the period ( as atomic num(er increases) due to the increasing nuclear charge. o It (ecomes easier to remo,e an electron do&n the group as the electron is further from the nucleus and more shielded (' the inner shells of electrons. o It (ecomes harder to remo,e each successi,e electron (ecause once an electron is remo,ed from the atom, the atom (ecomes positi,el' charged so the electrons left on (the ones 'ou are tr'ing to remo,e) are ,er' strongl' attracted to the atom. o %here is a (ig =ump in IE &hen an electron is remo,ed from a full outer shell eg. Aluminium has 3 electrons in its outer shell so the 6th IE is much (igger than the 3rd (ecause an electron is (eing remo,ed from a full shell. First IE: X(g) goes to X+(g) + eSecond IE: X+(g) goes to X2+(g) + eThird IE: X2+(g) goes to X +(g) + eFourth IE: X +(g) goes to X!+(g) + e-

0edo/
$I50I> $/idation is losing (electrons) reduction is gaining (electrons). $/idation is an increase in o/idation states 0eduction is a decrease in o/idation states $/idising agents are reduced (decrease in o/idation states) 0educing agents are o/idised (increase in o/idation states) o ?$/'anions@ are negati,e ions that contain o/'gen and another element. %heir names end in ?ate@ eg.sulfate. %he' should include an o/idation state in their name. o $/idation states should (e included in names &hen the elements in the compound can e/ist in more than one o/idation state. Eg. 2e$ is called iron(II) o/ide (ecause $@s o/idation state is 2 so 2e@s o/idation state must (e +2. o .alf equations for redo/ are as follo&s. o If the element has (een o/idised the electron goes on the right o If it@s (een reduced, the electron goes on the left. o %hin: reduced, right. !ut then s&itch it aroundA A higher (more reacti,e) halogen o/idises a lo&er (less reacti,e) halide. Eg. )l2(g) + 2I (aq) goes to 2)l (aq) + I2(aq) %his can (e split into 2 half equations+ )l2(aq) +2e goes to 2)l (aq)reduction 2I (aq) goes to I2(aq) + 2e o/idation Bisproportionation In some redo/ reactions, it is the same element that is simultaneousl' o/idised and reduced. %his is called disproportionation. %his occurs &hen the products consist of 2 forms of the disproportionised element.

%he .alogens
3h'sical properties
Flourine+ 3ale 'ello& gas, reacts &ith &ater, solu(le in organic sol,ents. "hlorine+ 3ale green gas, slightl' solu(le in &ater and organic sol,ents to gi,e a pale green solution. For#s a $hite %reci%itate o& silver chloride $ith silver ions' (ro#ine+ dar: red liquid, forms a (ro&n gas on &arming. Solu(le in &ater and organic sol,ents to gi,e red (ro&n and red solutions respecti,el'. For#s a crea# %reci%itate o& silver bro#ide $ith silver ions' Iodine+ Shin' (lac: solid, su(limes on &arming to gi,e a purple ,apour, (arel' solu(le in &ater to gi,e (ro&n solution, solu(le in organic sol,ents to gi,e ,iolet solution. For#s a )ello$ %reci%itate o& silver iodide $ith silver ions' o %he intramolecular (onds in the halogens are co,alent and the intermolecular (onds are IB IB (onds. o As the siCe of the molecule increases, so does the strength of the IB IB (onds, as there are more electrons. o %his e/plains &h' the halogens change from gas to liquid to solid do&n the group. o 0eacti,it' decreases do&n the group (ecause the halogens get (igger do&n the group sot the outer electrons are less attracted to the nucleus. o .alogens onl' displace (o/idise) lo&er halides. o %he general reaction of a halogen &ith sil,er ions is+ Ag+(aq) +8 (aq) goes to Ag8(s) o In redo/, halogens act as o/idising agents (decrease o/idation states D remo,e electrons from other elements) 82 + 2e goes to 28 o )hlorine is used in &ater treatment, to ma:e (leach, .)l and plastics. It is highl' to/ic so is transported road or rail tan:er as a liquid.

o !romine is used to ma:e flame retardants, agricultural fumigants and in photograph'. It@s transported in lead lined steel tan:s in metal frames. %ransport routes a,oid residential areas and it is often transported at night.

S3B2
Elements are split into num(er shells < 6, these are split up into su( shells, s, p, d and f. S su( shells ha,e < or(ital and can hold 2 electrons 3 su( shells ha,e 3 or(itals and can hold * electrons B su( shells ha,e E or(itals and can hold <# electrons. o $r(itals fill &ith one electron in each (efore going (ac: and putting 2 electrons in each or(ital. o $r(itals &ith < electron in ha,e parallel spins. o $r(itals &ith 2 electrons in ha,e opposite spins. * *s 2 2s

! 6s is al&a's filled (efore 3d (ecause it has a lo&er energ' and the su( shells are filled in order of increasing energ'. Also, the d shells prefer to (e e/actl' half full or completel' full eg. 3dE or 3d<# rather than 3dF (ecause this is lo&er energ', this therefore sometimes lea,es the 6s shell half full.

If the last electron in the element entered the s su( shell, it is said to (e in the ?s (loc:@ of the periodic ta(le. %his is also true of the other 3 (loc:s, p, d and f.

)hemical 1anufacturing
E/tracting !romine from sea &ater o 3artiall' e,aporated, acidified sea &ater is &armed and chlorine is added. It needs to (e acidified as sea &ater is naturall' slightl' al:aline and (oth chlorine and (romine dissol,e in al:ali. o Steam is (lo&n through the product. !romine is gi,en off as it is ,olatile. o %he ,apours are condensed and as (romine is not ,er' solu(le in &ater, t&o la'ers are formed. o %he (romine is distilled and dried.

!atch Gs )ontinuous 3rocessH

!atch. %he starting materials are put into a ,essel and allo&ed to react together. %he reaction is monitored and &hen complete, is terminated. %he product is then separated from the mi/ture. %he process is repeated (atch (' (atch.

)ontinuous. %he starting materials are fed in at one end and &ithdra& at the other in a continuous flo&.

(atch
Ad,antages
o o o o )ost effecti,e for small quantities Slo& reactions are catered for A range of products can (e made in the same ,essel A greater I con,ersion for the same amount in the same time than &ith continuous

Bisad,antages
o )harging and empt'ing the ,essel is time consuming as is hut do&n time. o 5arger &or:force needed than continuous o )ontamination is more li:el' as the same ,essel is used for different reactions. o E/othermic processes are difficult to control

"ontinuous
Ad,antages
o o o o o o o Suited to high tonnage >reater throughput and no need to shut do&n 1ore controlled as ,er' fine ad=ustment is possi(le )ontamination is less li:el' as is onl' used for one reaction )onsistent qualit' is ensured 1inimal &or:force and la(our needed 1ore easil' automated

Bisad,antages
o 1uch larger capital cost (start up costs) than (atch o Not cost effecti,e if run (elo& capacit' o )ontamination ris: is ,er' high if used for t&o or more products.

>reen )hemistr' aims to reduce the use of feedstoc:s to a minimum eg. 0ec'cle unused reactants and sol,ents and increase atom econom'. 0educe energ' consumption eg. 9se enC'mes to reduce temperature needed or :eep no. of steps to a minimum. 1inimise &aste D rec'cle or find &a's to ma:e use of &aste products. )o products are produced at the same time as the desired product ,ia the same reaction. As the amount of desired product increases, so does the amount of co products. )o products can (e sold for further profit. !' products are the result of un&anted side reactions. %he conditions of an' chemical process are designed to increase the amount of desired product and decrease the amount of (' products.

%he )hloral:ali 3rocess

%he mercur' cell %his is (eing phased out (' 2#2# (ecause it ,er' e/pensi,e to run and produces to/ic mercur' emissions. %he mem(rane cell Ad,antages+ o lo&er running costs than mercur' as less energ' used per tonne of chlorine produced. o 5arger capacit' for chlorine in the same space than mercur' cell o No need to remo,e to/ic mercur' from the products. o 5ess en,ironmental pollution. 0eaction at the positi,e anode+ 2)l goes to )l2 +2e 0eaction at negati,e cathode+ 2.2$ +2e goes to 2$. +.2 $,erall reaction+ 2)l +2.2$ goes to )l2 +2$. +.2

%he mem(rane is made from the 3%2E pol'mer and has negati,el' charged side chains &hich the Na+ ions are attracted to. %hese side chains repel )l and $. ions. Some &ater molecules are attached to the sodium ions and pass through (ut the mem(rane is impermea(le to free &ater molecules. %he cell is designed to+ o 3re,ent chlorine from reacting &ith $. o 1inimise )l ions diffusing into the negati,e electrode o 1inimise the $. ions from diffusing into the positi,e electrode o 3re,ent h'drogen and chlorine from mi/ing (ecause the mi/ture is e/plosi,e.

I 'ield and atom econom'

I 'ield J actual mass of product %heoretical ma/imum mass of product

/<##

%his measures the efficienc' of the reaction in terms of &aste and ho& much of the theoretical product is actuall' produced. I Atom econom' J 1r of useful product 1r of all reactants

/<##

%his measures the efficienc' of the reactants in the process and ho& much ends up in the products.

%itration )alculations
<dm3 J <###cm3 so to get from dm3 from cm3, di,ide cm3 (' <###.

Steps for titrations calcs+ <. &rite out (alanced equation 2. &or: out no. of moles (nJc / ,) of one 'ou :no& c and , for. 0emem(er to di,ide , (' <### to change to dm3. 3. &rite do&n mole ratio, if <+< s:ip to ne/t step. If the ?n@ 'ou =ust &or:ed out in step < is the smaller ratio then times ?n@ (' the (igger mole ratio for the ne/t purposes. If ?n@ is the larger of the 2 then di,ide (' the larger mole ratio.

6. carr' out cJnK, using 'our pre,iousl' &or:ed out ?n@ ,alue and the ?,@ gi,en in the question (remem(er to change it into dm3 so 2E cm3 is #.#2E dm3)

Intermolecular !onds
o bond %olarit) depends on the electronegati,it' difference (et&een the atoms o #olecular %olarit) depends on the electronegati,it' difference and the shape of the molecule. If molecule contain a N$2 atom and are not s'mmetrical, the' are li:el' to contain a 3B 3B (ond.

IB IB (onds
%hese occur in all molecules and are the &ea:est t'pe of intermolecular (onds. !ond enthalp' A Bipole occurs &hen a molecule has a positi,e end and a negati,e end -hen a molecule has a dipole &e sa' it is polarised. If a molecule has a permanent dipole it is called a polar molecule. %he constant mo,ement of electrons in a molecule means that at an' one time the electron densit' ma' (e une,enl' distri(uted, this creates an instantaneous dipole. %he polarit' of the molecule ma' change (ecause the electron densit' is constantl' mo,ing. If other molecules are close to the molecule &ith a dipole then electrons get attracted to the positi,e end of the original molecule, this induces a dipole in the ne& molecule. %he instantaneous dipole and the induced dipole attract each other. IB IB (onds are continuousl' forming and (rea:ing (ecause of the constant mo,ement of electrons &ithin the molecules. %he (igger the molecule, the more electrons it has so the greater the attraction and the strength of the IB IB (ond so the higher the (oiling point.

o A (igger molecule also has a larger surface area so has more points of contact &ith neigh(ouring molecules. o A long chain molecule has stronger IB IBs (ecause it has more points of contact. o A straight chain molecule has stronger IB IBs than a (ranched chain (ecause it can line up more closel' so has more points of contact. 3ol'(ethene) contains onl' IB IB (onds (ut is solid at room temperature. %his is (ecause the chains are long and can pac: close together meaning that there are man' IB IB (onds &hich compensates for their &ea:ness.

3B 3B (onds
o 1olecules &ith 3B 3B (onds contain atoms &ith different electronegati,it' ,alues. o %he partiall' positi,e end of one molecule attracts the partiall' negati,e end of the other. o 3B 3B (onds are stronger than IB IB (onds (ut &ea:er than h'drogen (onds. o 3B 3B (inds hold pol'ester molecules together. o $ccurs if the molecule is not s'mmetrical and the dipole moments don@t cancel each other out. o 3B 3B (onds can also induce dipoles in neigh(ouring molecules. Electronegati,it' is the a(ilit' of an atom to attract the (onding electron in a co,alent (ond %he (igger the difference in electronegati,it' a molecule has, the more ionic it is.

.alogenoal:anes
o %he homologous series of a halogenoal:ane is 0 8 or 0 .al &here 8 (.al) is a halogen D )l, !r or I. o All halogenoal:anes are immisci(le &ith &ater. o %he larger the halogen the higher the (oiling point (ecause there &ill (e stronger IB#IB (onds (et&een the molecules.

.omol'tic 2ission
o %his forms radicals of (oth the al:ane and the halogen. o %he condition is radiation of the right frequenc' (,isi(le or 9G) &hich is a(sor(ed (' the halogenoal:anes. o %his :ind of reaction occurs &hen halogenoal:anes reach the stratosphere &hich is &hat forms chlorine radicals.
o ).3 )l + h, goes to ).3 +)l

'

'

o $ne electron goes to each atom

.eterol'tic 2ission
o In .eterol'tic fission, the halogenoal:anes tend to react in a polar sol,ent such as ethanol, or ethanol and &ater. %his is the condition. o No radiation is needed in this process and no radicals are formed. o Instead a negati,e halide ion and a positi,e car(ocation are formed (' the complete (rea:age of the ) .al (ond. o .ere, (oth electrons go to the halogen to form a halide ion. o %he reaction is as follo&s+

0eacti,it' trends
o Strength of ) .al (ond decreases do&n the group (ecause the siCe of the halogen atom increases. o %herefore reacti,it' increases. o !ond strength rather than polarit' has the greatest effect on the reacti,it' of the halogenoal:anes. o %his is &h' !r (onds (rea: do&n in the troposphere &hereas )l (onds onl' (rea: do&n in the stratosphere, &rea:ing ha,oc on the oCone la'er.

Nucleophilic su(stitution reactions

o %he general equation &here 8 is a nucleophile is as follo&s+ 0 .al + 8 goes to 0 8 + .al o %he ) .al (ond (rea:s and the halogen atom is replaced (' the nucleophile. o %he mechanism for the Nucleophilic su(stitution of a halogenoal:anes is as follo&s+

o %he ) I (ond is polar so the car(on atom has a partiall' + charge and the iodine atom has a partiall' D charge. o %he $. ion is negati,el' charged so the o/'gen is attracted to the partiall' positi,e ) atom. o A lone pair of electrons mo,e from the o/'gen atom to the car(on atom as the ) I (ond (rea:s. o Iodine ions are formed, ho&e,er a free car(ocation is not formed (ecause the $. attac:s at the same time that the ) !r (ond (rea:s. + nucleo%hile is a #olecule or negativel) charged ion $ith a lone %air o& electrons that it can donate to a %ositivel) charged ato# to &or# a covalent bond'

All halogens ha,e 3 lone pairs %he negati,el' charged atom in the nucleophile al&a's donates the lone pair.

-ater as a Nucleophile
o %he reaction &ith &ater as nucleophile is slo&er (ecause &ater does not ha,e a full negati,e charge. o %he reaction happens in t&o stepsL first the &ater attac:s the halogenoal:ane in much the same &a' as a normal nucleophile.

o %he second step in,ol,es the resulting positi,el' charged ion from the first step, loses .+ to form an alcohol.

o %he o,erall equation for this reaction is+ 0 .al + .2$ goes to 0$. + .+ + .al o %his reaction can also (e done in re,erse to produce halogenoal:anes.

0.al + $. 0.al + .2$ 0.al + N.3 0$. + .al

"onditions .eat under reflu/ &ith Na$.(aq). $ften ethanol is added as a sol,ent .eat under reflu/, sometimes called h'drol'sis. %he halogenoal:ane is heated &ith concentrated ammonia in a sealed tu(e. In presence of a strong acid.

3reparation of halogenoal:anes
)arr'ing out the reaction o -eigh Eg of 2 meth'lpropan 2 ol and pour into a separating funnel. o >raduall' add 2#cm3 of concentrated .)l o Sha:e the mi/ture in the separating funnel for 2# minutes releasing the pressure from time to time. Separating the required product from the reaction mi/ture o Allo& the mi/ture to stand until the 2 la'ers ha,e separated. %he alcohol ().3)3)$. &ill (e on the (ottom and ().3)3))l &ill (e on the top la'er. o %o remo,e the e/cess acid, add sodium h'drogen car(onate solution (ut (e careful to release the pressure as car(on dio/ide is formed. 0un off the lo&er aqueous la'er. 0epeat until no more gas is gi,en off. o Add <#cm3 distilled &ater and run off aqueous la'er again. o 0un organic ((ottom) la'er ().3)3))l into a clean conical flas:. o Add anh'drous sodium sulphate (a dr'ing agent) to remo,e an' traces of &ater. 3urif'ing the product o %he mi/ture is transferred to a flas: and then distilled.

Na#e .'dro/ide ion )'anide ion Ethanoate ion

For#ula $. )N ).3)$$

Structure

Etho/ide ion

)2.E$

-ater molecule Ammonia molecule

.2$ N.3